CN115746658A - Polyurethane and inorganic salt dual-modified epoxy emulsion and preparation method thereof - Google Patents
Polyurethane and inorganic salt dual-modified epoxy emulsion and preparation method thereof Download PDFInfo
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- CN115746658A CN115746658A CN202211363746.XA CN202211363746A CN115746658A CN 115746658 A CN115746658 A CN 115746658A CN 202211363746 A CN202211363746 A CN 202211363746A CN 115746658 A CN115746658 A CN 115746658A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 121
- 239000004593 Epoxy Substances 0.000 title claims abstract description 107
- 239000004814 polyurethane Substances 0.000 title claims abstract description 60
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 60
- 229910017053 inorganic salt Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000004945 emulsification Methods 0.000 title description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003822 epoxy resin Substances 0.000 claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012874 anionic emulsifier Substances 0.000 claims abstract description 9
- 239000006184 cosolvent Substances 0.000 claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 9
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 9
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 238000010008 shearing Methods 0.000 claims description 17
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 238000009396 hybridization Methods 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004111 Potassium silicate Substances 0.000 claims description 5
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 5
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- -1 hydroxy acid salt Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000003595 mist Substances 0.000 abstract description 2
- 239000003995 emulsifying agent Substances 0.000 description 33
- 239000007787 solid Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 10
- 238000011161 development Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000007385 chemical modification Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 238000000614 phase inversion technique Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 235000006487 Euryale ferox Nutrition 0.000 description 1
- 244000268590 Euryale ferox Species 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ZTFZSHLWORMEHO-UHFFFAOYSA-A pentaaluminum;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ZTFZSHLWORMEHO-UHFFFAOYSA-A 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses polyurethane and inorganic salt double-modified epoxy emulsion and a preparation method thereof. The polyurethane and inorganic salt double-modified epoxy emulsion is prepared from the following raw materials in parts by weight: 50-70 parts of first epoxy resin; 0.01-0.04 part of catalyst, 80-100 parts of second epoxy resin, 5-9 parts of isocyanate, 12-17 parts of non-ionic emulsifier, 3-7 parts of anionic emulsifier, 5-15 parts of cosolvent, 5-10 parts of silicate solution and 100-130 parts of water. The polyurethane and inorganic salt double modified epoxy emulsion has the advantages of good salt mist resistance, acid and alkali resistance, flexibility and the like, and the preparation process of the polyurethane and inorganic salt double modified epoxy emulsion is simple.
Description
Technical Field
The invention relates to an epoxy emulsion, in particular to a polyurethane and inorganic salt double-modified epoxy emulsion and a preparation method thereof.
Background
With the development of coating science and technology and new ideas and law consciousness of people, higher and higher requirements on environmental protection are put forward. Because the organic solvent volatilized from the traditional solvent-based paint brings serious adverse effects on air pollution and human health, the development towards low VOC, high efficiency, energy saving and ecological directions, and the research and development of environment-friendly high-performance paint becomes a consensus of the paint industry and is a necessary way for the development of the paint industry.
Epoxy resins have been widely used in military, civil, and industrial maintenance applications due to their excellent properties, such as good adhesion, good chemical resistance, excellent solvent resistance, high hardness, good wear resistance, and the like. In particular in coating applications, currently 40% of the epoxy resins are used in coatings worldwide. The epoxy resin is not dissolved in water, can not be directly added with water for emulsification, and is prepared by introducing a hydrophilic chain segment or adding a hydrophilic component into a molecular chain, and the preparation of the epoxy resin into an emulsion is a technical path with the highest application value.
The epoxy resin is hydrated by the following three methods: mechanical methods, phase inversion methods and chemical modification methods. The mechanical method is also called direct emulsification method, and refers to that epoxy resin is ground in a ball mill, then an aqueous solution of an emulsifier is added, and particles are uniformly dispersed in water through mechanical stirring. The phase inversion method refers to a process of mutual conversion under a certain condition in a multi-component system, and almost all polymer resins can be prepared into corresponding emulsion by a physical emulsification method under the action of an external emulsifier, but the defects are that the stability of the emulsion is poor, the water-based epoxy curing agent, the filler and various auxiliaries are greatly influenced when the water-based epoxy curing agent, the filler and the various auxiliaries are matched for use, and the existence of the external emulsifier also has a certain influence on the performance of a coating film. The self-emulsifying method is a chemical modification method, the size of dispersed phase particles in the aqueous epoxy resin emulsion prepared by the chemical modification method is very small, about dozens to hundreds of nanometers, and the chemically modified epoxy resin contains hydrophilic polar groups which can help the epoxy resin to disperse in water, so that the modified resin has the amphiphilic property of hydrophilic poise and has the effect of a surfactant. When the modified polymer is emulsified by the saliva, the molecular chains of the hydrophobic polymer are aggregated into particles, and the stable water-based epoxy resin emulsion can be formed.
The research on polyurethane modified epoxy resin or epoxy resin modified polyurethane has been long in the past, and many related reports exist in China, for example, a patent CN101445583A discloses a preparation process of polyurethane modified epoxy resin suitable for a composite wear-resistant coating material, polyurethane modified solvent type epoxy resin is adopted, and a paint film prepared by introducing a polyurethane prepolymer into the epoxy resin has excellent characteristics. However, the research is only an improvement on the performance of the coating, and the product does not meet the development trend of coating industry at home and abroad and does not meet the requirements of low pollution or no pollution. In the field of waterborne coatings, epoxy resin modified waterborne polyurethane is mostly seen, and the aim is to enable a waterborne polyurethane system to be more suitable for the development requirement of the coating industry, and the branching points are introduced into a polyurethane main chain by utilizing the advantages of high modulus, high strength, good chemical resistance and the like of epoxy resin to enable the polyurethane main chain to form a partial network structure. For example, articles ("development of waterborne epoxy modified polyurethane coatings" in the Gorgon et al, coatings INDUSTRY, 1998; polyurethane-modified waterborne epoxy resins are reported, for example, in an article ("waterborne polyurethane-modified epoxy curing agent", liu Han Jie et al, coatings industry, vol. 34, no. 2, 2003-11-09) to improve the coating properties of epoxy resins by toughening the epoxy resins with polyurethanes.
In summary, the water-based preparation of epoxy resin and the modification of polyurethane epoxy resin are feasible, but at present, no patent is found about the method for preparing polyurethane modified, emulsified and nano water-based epoxy emulsion, and the method for modifying epoxy emulsion by inorganic salt is less mentioned. The invention systematically and organically combines epoxy resin emulsification, polyurethane modified waterborne epoxy resin, inorganic salt modified epoxy emulsion and nanocrystallization of epoxy resin, and provides a preparation method of polyurethane and inorganic salt double-modified waterborne epoxy emulsion.
Disclosure of Invention
The invention aims to provide a polyurethane and inorganic salt double-modified epoxy emulsion and a preparation method thereof. The polyurethane and inorganic salt double modified epoxy emulsion has the advantages of good salt mist resistance, acid and alkali resistance, flexibility and the like.
In order to solve the defects of the prior art, the technical scheme adopted by the invention is as follows:
the invention provides a polyurethane and inorganic salt double-modified epoxy emulsion which is prepared from the following raw materials in parts by weight:
50-70 parts of first epoxy resin; 0.01-0.04 part of catalyst, 80-100 parts of second epoxy resin, 5-9 parts of isocyanate, 12-17 parts of non-ionic emulsifier, 3-7 parts of anionic emulsifier, 5-15 parts of cosolvent, 5-10 parts of silicate solution and 100-130 parts of water.
Preferably, the polyurethane and inorganic salt double-modified epoxy emulsion is prepared from the following raw materials in parts by weight:
55-65 parts of first epoxy resin, 0.01-0.04 part of catalyst, 87-95 parts of second epoxy resin, 5-8 parts of isocyanate, 13-15 parts of nonionic emulsifier, 4-7 parts of anionic emulsifier, 8-15 parts of cosolvent, 6-8 parts of silicate solution and 110-120 parts of water
Further, in the polyurethane and inorganic salt double-modified epoxy emulsion, the first epoxy resin is composed of one or a mixture of E51, E44 and E31.
Further, in the polyurethane and inorganic salt double-modified epoxy emulsion, the second epoxy resin is composed of one or more of E20, E12 and E06.
Further, the polyurethane and inorganic salt double modified epoxy emulsion is characterized in that the isocyanate is composed of one or a mixture of IPDI, TDI and MDI.
Further, the polyurethane and inorganic salt double modified epoxy emulsion is characterized in that the nonionic emulsifier is composed of one or a mixture of polyether type, polyester type and polyurethane type.
Further, the polyurethane and inorganic salt double modified epoxy emulsion comprises one or a mixture of sulfonate, hydroxy acid salt and sulfate as an anionic emulsifier.
Further, in the polyurethane and inorganic salt double modified epoxy emulsion, the silicate solution is composed of one or a mixture of potassium silicate, lithium silicate and calcium silicate.
Further, in the polyurethane and inorganic salt double-modified epoxy emulsion, the catalyst is dibutyltin dilaurate; the cosolvent is composed of one or more of PM, DPNB, BCS and DBE.
The second aspect of the present invention provides a preparation method of the polyurethane and inorganic salt double modified epoxy emulsion, which comprises the following steps:
s1, adding first epoxy resin, a catalyst and isocyanate into a four-neck flask with a condensing tube according to parts by weight, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h;
s2, adding a second epoxy resin and a cosolvent into a four-neck flask while stirring, keeping the temperature at 80 ℃, and mixing for 0.5h;
s3, adding a nonionic emulsifier and an anionic emulsifier into the four-neck flask while stirring, keeping the temperature at 80 ℃, and stirring for 2 hours;
and S4, removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is dripped within 1.5 h. Obtaining epoxy emulsion;
s5, adding silicate into the epoxy emulsion under the stirring state, heating to 60 ℃, and carrying out hybridization reaction for 2 hours to prepare the double modified epoxy emulsion.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention has the beneficial effects that: the polyurethane and inorganic salt double-modified epoxy emulsion has the advantages of good salt spray resistance, acid and alkali resistance, flexibility and the like, the salt spray resistance can reach more than 1500h under the coating thickness of 60 mu m, and the flexibility can reach 1mm, which is difficult to achieve under the condition of single polyurethane modification. The polyurethane and inorganic salt double-modified epoxy emulsion disclosed by the invention is simple in preparation process, relatively mild in temperature in the preparation process, and excessive adjustment of the existing production equipment of the unmodified emulsion is not required in the subsequent production process.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way.
The reagents, methods and apparatus used in the following examples are conventional in the art, unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
The preparation method of the polyurethane and inorganic salt double-modified epoxy emulsion of the embodiment is as follows:
adding 51-55g of E, 0.01g of catalyst and 6g of IPDI into a four-neck flask with a condenser tube, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h.
While stirring, E12-94g and PM-8g were added to a four-necked flask, and the mixture was kept at 80 ℃ and mixed for 0.5 hour.
13g of polyether emulsifier and 4g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 6g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Example 2
The preparation method of the polyurethane and inorganic salt double-modified epoxy emulsion of the embodiment is as follows:
adding 51-60g of E, 0.02g of catalyst and 5g of IPDI into a four-neck flask with a condenser tube, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h.
While stirring, E12-90g and PM-11g were added to a four-necked flask, and the mixture was kept at 80 ℃ and mixed for 0.5 hour.
14g of polyether emulsifier and 5g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water into the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃, so that all water is completely dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 8g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Example 3
The preparation method of the polyurethane and inorganic salt double-modified epoxy emulsion of the embodiment is as follows:
adding 31-64g of E, 0.04g of catalyst and 8g of IPDI into a four-neck flask with a condenser, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h.
While stirring, E12-94g and PM-14g were added to a four-necked flask, and the mixture was kept at 80 ℃ for 0.5 hour.
15g of polyether emulsifier and 7g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 8g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Example 4
The preparation method of the polyurethane and inorganic salt double-modified epoxy emulsion of the embodiment is as follows:
adding E31-60g, catalyst 0.04g and MDI-7.9g into a four-neck flask with a condenser tube, mixing for 15min at 60 ℃, slowly heating to 80 ℃ and reacting for 2h.
20-87g of E and 5g of DPNB were added to a four-necked flask while stirring, and the mixture was kept at 80 ℃ and mixed for 0.5 hour.
14g of polyether emulsifier and 6g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water into the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃, so that all water is completely dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 7g of potassium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Example 5
The preparation method of the polyurethane and inorganic salt double-modified epoxy emulsion of the embodiment is as follows:
adding 31-65g of E, 0.04g of catalyst and 8g of IPDI into a four-neck flask with a condenser, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h.
While stirring, E12-90g and DBE-9g were added to a four-necked flask, and the mixture was kept at 80 ℃ and mixed for 0.5 hour.
14g of polyether emulsifier and 4g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 6g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Example 6
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion of the embodiment is as follows:
adding 51-60g of E, 0.04g of catalyst and 8g of MDI into a four-neck flask with a condenser, mixing for 15min at 60 ℃, slowly heating to 80 ℃ and reacting for 2h.
Into a four-necked flask were added 20 to 87g of E and 15g of PM while stirring, and the mixture was kept at 80 ℃ for 0.5 hour.
14g of polyether emulsifier and 5g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 8g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Example 7
The preparation method of the polyurethane and inorganic salt double-modified epoxy emulsion of the embodiment is as follows:
adding E31-70g, catalyst 0.03g and MDI-9g into a four-neck flask with a condenser tube, mixing for 15min at 60 ℃, slowly heating to 80 ℃ and reacting for 2h.
12-80g of E and 9g of DPNB were added to a four-necked flask while stirring, and the mixture was kept at 80 ℃ for 0.5 hour.
While stirring, 12g of polyester emulsifier and 3g of sulfonate emulsifier are added into a four-neck flask, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 5g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Example 8
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion of the embodiment is as follows:
adding E51-59g, catalyst 0.04g and IPDI-7g into a four-neck flask with a condenser tube, mixing at 60 deg.C for 15min, slowly heating to 80 deg.C, and reacting for 2h.
While stirring, E12-90g and DBE-5g were added to a four-necked flask, and the mixture was kept at 80 ℃ and mixed for 0.5 hour.
13g of polyether emulsifier and 7g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water into the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃, so that all water is completely dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the condition of stirring, 10g of potassium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Example 9
The preparation method of the polyurethane and inorganic salt double-modified epoxy emulsion of the embodiment is as follows:
adding 31-60g of E, 0.04g of catalyst and 7.5g of IPDI into a four-neck flask with a condenser tube, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h.
Into a four-necked flask were added 20 to 95g of E and 10g of PM while stirring, and the mixture was kept at 80 ℃ for 0.5 hour.
17g of polyether emulsifier and 3g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 9g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Example 10
The preparation method of the polyurethane and inorganic salt double-modified epoxy emulsion of the embodiment is as follows:
adding 51-62g of E, 0.04g of catalyst and 7.4g of IPDI (isophorone diisocyanate) into a four-neck flask with a condenser, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h.
While stirring, E12-91g and DPNB-10g were added to a four-necked flask, and the mixture was kept at 80 ℃ and mixed for 0.5 hour.
14.8g of polyester emulsifier and 6.7g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water into the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃, so that all water is completely dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 8g of potassium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Example 11
The preparation method of the polyurethane and inorganic salt double modified epoxy emulsion of the embodiment is as follows:
adding 51-60g of E, 0.03g of catalyst and 9g of IPDI into a four-neck flask with a condenser tube, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h.
While stirring, E12-95g and DBE-9g were added to a four-necked flask, and the mixture was kept at 80 ℃ and mixed for 0.5 hour.
15g of polyether emulsifier and 6g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 10g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Example 12
The preparation method of the polyurethane and inorganic salt double-modified epoxy emulsion of the embodiment is as follows:
adding E51-64.5g, catalyst 0.04g and IPDI-7.4g into a four-neck flask with a condenser tube, mixing at 60 deg.C for 15min, slowly heating to 80 deg.C, and reacting for 2h.
While stirring, E12-100g and PM-10g were added to a four-necked flask, and the mixture was kept at 80 ℃ for 0.5 hour.
17g of polyether emulsifier and 6g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water into the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃, so that all water is completely dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 8g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the double modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Comparative example 1
Adding E51-64.5g, E12-95g and PM-10g into a four-neck flask provided with a condenser tube, mixing for 15min at 60 ℃, adding 16g of polyether emulsifier and 6g of sulfonate emulsifier while stirring, slowly heating to 80 ℃, and stirring for 2h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is dripped within 1.5 h. Obtaining the epoxy emulsion.
The solid content of the emulsion is 60 percent.
Comparative example 2
Adding E51-64.5g, catalyst 0.04g and IPDI-7.4g into a four-neck flask with a condenser tube, mixing at 60 deg.C for 15min, slowly heating to 80 deg.C, and reacting for 2h.
While stirring, E12-95g and PM-10g were added to a four-necked flask, and the mixture was kept at 80 ℃ for 0.5 hour.
16g of polyether emulsifier and 6g of sulfonate emulsifier are added into a four-neck flask while stirring, and the mixture is stirred for 2 hours while keeping the temperature at 80 ℃.
And (3) removing the heating device, and slowly dripping water into the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃, so that all water is completely dripped within 1.5 h. Obtaining the epoxy emulsion.
And preparing the modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
Comparative example 3
Adding E51-64.5g, E12-95g and PM-10g into a four-neck flask provided with a condenser, mixing for 15min at 60 ℃, adding 16g of polyether emulsifier and 6g of sulfonate emulsifier while stirring, slowly heating to 80 ℃, and stirring for 2h.
And (3) removing the heating device, and slowly dripping water from the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃ so as to ensure that all water is dripped within 1.5 h. Obtaining the epoxy emulsion.
Under the stirring state, 8g of lithium silicate is added into the epoxy emulsion, the temperature is raised to 60 ℃, and the hybridization reaction is carried out for 2h.
And preparing the modified epoxy emulsion.
The solid content of the emulsion is 60 percent.
After the emulsion of all the examples is prepared, the waterborne epoxy anticorrosive primer is prepared by using the same formula, and the formula is shown in the following table 1:
TABLE 1 formula table of water-based epoxy anti-corrosive primer
| Composition of | Proportioning |
| Deionized water | 17 |
| Substrate wetting agent | 0.5 |
| Water-based anti-settling wax | 3 |
| Dispersing agent | 1 |
| Defoaming agent | 0.2 |
| Leveling agent | 0.2 |
| Zinc phosphate | 5 |
| Aluminium triphosphate | 9 |
| Titanium white powder | 14 |
| Barium sulfate | 9 |
| Epoxy emulsion | 60 |
| Aqueous epoxy curing agent | 30 |
Test example
The anticorrosion primers prepared by using the epoxy emulsions of examples 1 to 12 and comparative examples 1 to 3 as raw materials were subjected to performance tests according to the established standards, the tests are shown in Table 2 according to the standards, and the test results are shown in Table 3:
TABLE 2 Performance test standards
| Main technical parameters | Test standard |
| Flexibility of the film | GB/T1731-1993 |
| Acid resistance | GB/T1763 |
| Alkali resistance | GB/T1763 |
| Resistance to salt fog | GB/T1771-2007 |
TABLE 3 results of performance test of epoxy anticorrosive primers prepared in examples 1 to 12 and comparative examples 1 to 3
As can be seen from Table 3: the water-based anticorrosive primer prepared from the polyurethane and inorganic salt double-modified epoxy emulsion has better salt spray resistance, acid and alkali resistance and flexibility than other modified products. Especially the salt spray resistance can reach more than 1500h and the flexibility can reach 1mm under the condition that the coating thickness is 60 mu m.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A polyurethane and inorganic salt double modified epoxy emulsion is characterized in that: the feed is prepared from the following raw materials in parts by weight:
50-70 parts of first epoxy resin; 0.01-0.04 part of catalyst, 80-100 parts of second epoxy resin, 5-9 parts of isocyanate, 12-17 parts of non-ionic emulsifier, 3-7 parts of anionic emulsifier, 5-15 parts of cosolvent, 5-10 parts of silicate solution and 100-130 parts of water.
2. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1, wherein: the feed is prepared from the following raw materials in parts by weight:
55-65 parts of first epoxy resin, 0.01-0.04 part of catalyst, 87-95 parts of second epoxy resin, 5-8 parts of isocyanate, 13-15 parts of nonionic emulsifier, 4-7 parts of anionic emulsifier, 8-15 parts of cosolvent, 6-8 parts of silicate solution and 110-120 parts of water.
3. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1 or 2, characterized in that: the first epoxy resin is composed of one or a mixture of E51, E44 and E31.
4. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1, wherein: the second epoxy resin is composed of one or more mixtures of E20, E12 and E06.
5. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1 or 2, characterized in that: the isocyanate is composed of one or a mixture of IPDI, TDI and MDI.
6. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1 or 2, characterized in that: the non-ionic emulsifier is composed of one or a mixture of polyether type, polyester type and polyurethane type.
7. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1 or 2, characterized in that: the anionic emulsifier is composed of one or a mixture of sulfonate, hydroxy acid salt and sulfate.
8. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1 or 2, characterized in that: the silicate solution is composed of one or a mixture of potassium silicate, lithium silicate and calcium silicate.
9. The polyurethane, inorganic salt double modified epoxy emulsion of claim 1 or 2, characterized in that: the catalyst is dibutyltin dilaurate; the cosolvent is composed of one or more of PM, DPNB, BCS and DBE.
10. A preparation method of polyurethane and inorganic salt double modified epoxy emulsion is characterized by comprising the following steps: the method comprises the following steps:
s1, adding first epoxy resin, a catalyst and isocyanate into a four-neck flask with a condensing tube according to parts by weight, mixing for 15min at 60 ℃, slowly heating to 80 ℃, and reacting for 2h;
s2, adding a second epoxy resin and a cosolvent into a four-neck flask while stirring, keeping the temperature at 80 ℃, and mixing for 0.5h;
s3, adding a nonionic emulsifier and an anionic emulsifier into the four-neck flask while stirring, keeping the temperature at 80 ℃, and stirring for 2 hours;
and S4, removing the heating device, and slowly dripping water into the resin in a high-speed shearing state to perform phase inversion when the temperature is reduced to 60 ℃, so that all water is dripped within 1.5 hours. Obtaining epoxy emulsion;
s5, adding silicate into the epoxy emulsion under the stirring state, heating to 60 ℃, and carrying out hybridization reaction for 2 hours to prepare the double modified epoxy emulsion.
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| CN113278346A (en) * | 2021-06-03 | 2021-08-20 | 武汉工程大学 | Water-based epoxy resin emulsion for heavy-duty anticorrosive paint and preparation method and application thereof |
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